Process of making dipolymer



Patented Nov. 13, 1928. l

v 1,691,061 NI D- STATES PATENT OFFICE.

ravm W. mm, or WHARTON, NEW JERSEY, ASSIGNOR 'ro HERCULES rownEE column,or wnmmeron, DELAWARE, A CORPORATION OF DELAWARE.

PROCESS OF MAKING DIPOLY MER.

- The object of my invention is 'to produce Dipolymer.

Dipolymer, as the term is herein employed,

1 is a product, consisting of polymer zed terpene hydrocarbons, which isobtained ;by

polymerizing dipentene, turpentine, or plne oil. Although it is largelycomposed of the Dipolymer ('G H, substantial p'roportions ofhigherpolymers, (C H are generally present. Dipentene, as the term is 'hereinemployed, refers to the cut of pine products boiling largely between 165and 185 0., which is obtained in the steam distillation of pine wood.Pure dipentene boils at 1746 in used is intended to comprehend the crudeproduct with the wider boiling range.

. It is known to make Dipolymer,-in the liquid' phase, by treatingturpentine .or dlpentenewith sulfuric acid of various concentrations. Ihave discovered that it may be made, in the vapor phase, from dipentene,by a simple and economical new process.

Polymerization'of dipentene in the vapor phase may .be carried out, attemperatures ranging from 17555 0 Cl, by passing the vapors of dipentenethrough a tubeof iron or' other suitable material at such a rate as willpermit the vapors to remain in cont-a ct with a catalyst, filling orcontained'in the tube, long enough to cause a partial polymerization.For example, through an iron tube 28" x -1", heated to about 400 C.,containing 8'1O mesh fullers earth, is passed 200 cc. of 5 dipentene atthe rate of cc. per hour. There were recovered 164 cc. of a productcontaining 62 cc. of Dipolymer. A portion of the unpolymerized oil waspolymerized by repassing through the tube. The polymerization of thehydrocarbons of the dipentene to Dipolymer plus a proportion of thehigher polymers involves the following reaction:

= chlorides, such as the chlorides of zinc, tin,

aluminum and iron, as well as other polymerizin agents, ma besubstituted for fullers ear%, or minera earth may be impregnated 3Application filed July 20,

C;, but the term dipentene as here 1923. Serial No. 123,816.

operating at a lower temperature; and the conversion in'vapor phasepresents, in some material respects, distinct advantages.

The crude product 'WhlCll. is obtained on polymerizing dipentene may beemployed, in

some. instances, without refining; but it is usually preferable todistill off the lower boiling end, cutting around 250 C. By thisprocedure, the-hydrocarbons and any unaltered dipenteneare separated,leaving a residue consisting of crude Dipolymer.

A typical sample of crude Dipolymer has a specific gravity of 0.95, andthe following boilin range: 5% over at 305 0., 20% at 326- 90% at 375 C.If a cut is made when approximately 80% has distilled over, a product isobtained having 'a specific gravity of 0.94. A second cut may be madecomprising approximately the 80-95% portion of the crude Dipolymer. Thiscut is exceedingly viscous-and resembles a soft rosin. The

residue is hard and brittle and has the appearance of a dark coloredrosin.

. For some applications of the Dipolymer it may be deslrable to separateit into cuts as outlined above.

The polymerization of dipentene to Dipolymer by means of metallicchlorides presents certain peculiar advantages and forms thesubject-matter of a separate application. Having now fully described myinvention,

what I claim and desire to protect by Letters Patent is z 1. The processof preparing Dipolymer from dipentene which comprises vaporizingdipentene and passing the vapors in intimate contact with a catalyst forsuch length-of time and at such temperature as will 'efi'ect substantialpart of the polymerization of a the dipentene vapors.

'2. The process of preparing Dipolymer from dipentene which comprisesvaporizing dipentene and permeable catalyst for such length of time andat such temperature as will effect the polymerization of a substantialpart of the pine oilyapors. 1

., 50 at 335 0., 70% at 342 C. and

passing the vapors through a 3. The process of preparing Dipolymer fromdipentene which comprises passing the vapors of dipentene, while at atemperature above 175 C. and below 550 C., in intimate contact with acatalyst for such length of time as will eiiect the polymerization of asubstantial part of the dipentene vapors.

4. The process of preparing Dipolymer from dipentene which comprisespassing the Vapors of dipentene, while at a temperature above 17 5 C.and below 550 C., in intimate contactwith a catalyst for such length oftime as will efi'ect the polymerization of asubstantial part of thedipentene vapors, condensing the product, and reheating to a temperaturerequired to vaporize the lower boiling fractions of the same, leaving aresidue which comprises principally Dipolymer.

5. The process of preparing Dipolymer from dipentene which comprisespassing the vapors of dipentene, While at a temperature above 175 C. andbelow 550 0., in intimate contact with a catalyst for such length oftime as will eflect the polymerization of a substantial part of thedlpentene vapors, condensing the product, and fractionally distillingthe same at temperatures adapted to yield prod ucts having specificgravities progressively lower than .96.

6. The process of preparing Dipolymer from dipentene which comprisesvaporizing dipentene and passing the vapors in intimate contact withfullers earth for such length of time and at such temperature as willeifect the polymerization of a substantial part of the dipentene vapors.

7. The process of preparing Dipolymer from dipentene which comprisespassing the vapors of dipentene, while at a temperature of about 400 C.in intimate contact with a catalyst for such length of time as willefliect the polymerization of a substantial part of the dipentenevapors. v

In testimony of which invention, I have hereunto set my hand, atPhiladelphia, Pennsylvania, on this 2nd day of July, 1926.

TRVIN W. HUMPHREY

